Theτ-value for games on matroids

In the classical model of games with transferable utility one assumes that each subgroup of players can form and cooperate to obtain its value. However, we can think that in some situations this assumption is not realistic, that is, not all coalitions are feasible. This suggests that it is necessary to raise the whole question of generalizing the concept of transferable utility game, and therefore to introduce new solution concepts. In this paper we define games on matroids and extend theτ-value as a compromise value for these games. This work has been partially supported by the Spanish Ministery of Science and Technology under grant SEC2000-1243.     

Mass spectrometric characterization of glycated <Emphasis Type="Italic">β</Emphasis>-lactoglobulin peptides derived from galacto-oligosaccharides surviving the <Emphasis Type="Italic">in vitro</Emphasis> gastrointestinal digestion

A mass spectrometric study has been carried out to elucidate the structures of glycated peptides obtained after in vitro gastrointestinal digestion of bovine beta-lactoglobulin (beta-LG) glycated with prebiotic galacto-oligosaccharides (GOS). The digests of both native and glycated beta-LG were analyzed by MALDI-MS, LC-ESI-MS, and LC-ESI-MS/MS. MALDI-MS profiles showed marked differences mainly related to the lower intensity of ions corresponding to the digest of glycated beta-LG. Overall, 58 and 23 unglycated peptides covering 97% and 63% of the mature beta-LG sequence could be identified in the digests of native and glycated samples, respectively. The LC-ESI-MS analyses corroborated the MALDI-MS results regarding the unglycated peptides but they also enabled an extensive investigation into the digest of glycated beta-LG. Thus, a total of 19 peptides glycated with GOS from two to seven hexose units could be identified. The tandem mass spectra of glycated peptides were mostly characterized by two neutral losses of 1026/1056, 864/894, 702/732, 540/570, 378/408, and 216/246 u, corresponding to the formation of the furylium ion and its subsequent "CHOH" loss, indicative of the peptide glycation with hepta-, hexa-, penta-, tetra-, tri-, and disaccharides, respectively. Also, other minor ionic species containing the furylium ring linked to different galactose units could be also detected, showing the diversity of the fragmentation pattern of peptides glycated with larger size carbohydrates. Finally, the putative GOS glycation sites could be determined at the NH(2)-terminal Leu residue and at Lys residues located in positions 14, 47, 75, 77, 83, 91, 100, 135, and 138.     

Selective linkage detection of O‐sialoglycan isomers by negative electrospray ionization ion trap tandem mass spectrometry

Sialylated O‐linked oligosaccharides are involved in many biological processes, such as cell‐cell interactions, cell‐substance adhesion, and virus‐host interactions. These activities depend on their structure, which is frequently determined by tandem mass spectrometry. However, these spectra are frequently analyzer‐dependent, which makes it difficult to develop widely applicable analytical methods. In order to deepen the origin of this behavior, two couples of isomers of sialylated O‐linked oligosaccharides, NeuAcα2‐3Galβ1‐3GalNAc‐ol/Galβ1‐3(NeuAcα2‐6)GalNAc‐ol and NeuGcα2‐3Galβ1‐3GalNAc‐ol/Galβ1‐3(NeuGcα2‐6)GalNAc‐ol, were analyzed by liquid chromatography/negative electrospray ionization ion trap tandem mass spectrometry (LC/ESI(?)‐MSⁿ) using both an ion trap and a triple quadrupole mass spectrometer. Results clearly showed that while ions obtained in the triple quadrupole instrument fitted very well with the standard fragmentation routes, in the ion trap several intense ions could not be explained by these rules, specially a fragment at m/z 597. Furthermore, this ion was observed in the mass spectrum of those isomers that sialic acid binds to GalNAc by an α2‐6 linkage. From the MS³ spectrum of this ion an unexpected structure was deduced, and it led to propose alternative fragmentation pathways. Molecular mechanics calculations suggested that the found atypical route could be promoted by a hydrogen bond located only in α2‐6‐linked oligosaccharides. It has also been demonstrated that this process follows a slow kinetic, explaining why it cannot be observed using an ion beam‐type mass analyzer. In conclusion, ion traps seem to be more appropriate than triple quadrupoles to develop a reliable analytical method to distinguish between isomeric O‐linked glycans. Copyright © 2010 John Wiley & Sons, Ltd.     

Retention Indices of 55 Solutes Belonging to Eight Monofunctional Groups Homologous Series on 14 Chromatographic Capillary Columns

Retention indices, RI, of 55 solutes belonging to eight chemical monofunctional group series were computed at 373 K from retention factors measurements on 14 capillary columns coated with stationary phases, SP, spanning almost the whole polarity range. RI-values of some of these analytes were validated by comparison with literature values. Positive slope straight lines were obtained for the isothermal RI versus Z plots for the eight chemical functions. For a given series the slope (A) is rather insensitive to RP, while the intercept (FF) clearly increases linearly with increasing RP. For a given stationary phase A does not show any clear trend with increasing solute polarity, while FF increases clearly from the less polar to the most polar series.     

Values for Interior Operator Games

The aim of this paper is to study a new class of cooperative games called interior operator games. These games are additive games restricted by antimatroids. We consider several types of cooperative games as peer group games, big boss games, clan games and information market games and show that all of them are interior operator games. Next, we analyze the properties of these games and compute the Shapley, Banzhaf and Tijs values.     

Ultrafiltration as alternative purification procedure for the characterization of low and high molecular-mass phenolics from almond skins

A combination of sample preparation (ultrafiltration) and analysis techniques is proposed for the characterization of complex phenolic mixtures such as extracts from almond (Prunus dulcis (Mill.) D.A. Webb) skins. LC/ESI-MS analysis of the permeates obtained after ultrafiltration on semipermeable membranes (low molecular-mass phenolic fractions) allowed the identification of several benzoic acids and aldehydes, flavan-3-ol monomers and oligomers, and flavonol and flavanone glycosides in almond skins. MALDI-TOF and ESI-MS/MS analysis of the diafiltered concentrates (high molecular-mass phenolic fractions) demonstrated the presence of proanthocyanidin oligomers up to decamers, composed of (epi)afzelechin, (epi)catechin and (epi)gallocatechin units linked by CC bonds (type B) and by both CC and CO bonds (type A). This analytical protocol can be of utility in the study of low and high molecular-mass phenolic compounds in natural products.     

Single-wall carbon nanotube chemical attachment at platinum electrodes

Self-assembled monolayer (SAM) techniques were used to adsorb 4-aminothiophenol (4-ATP) on platinum electrodes in order to obtain an amino-terminated SAM as the base for the chemical attachment of single-wall carbon nanotubes (SWCNTs). A physico-chemical, morphological and electrochemical characterizations of SWCNTs attached onto the modified Pt electrodes was done by using reflection-absorption infrared spectroscopy (RAIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and cyclic voltammetry (CV) techniques. The SWNTs/4-ATP/Pt surface had regions of small, medium, and large thickness of carbon nanotubes with heights of 100-200 nm, 700 nm to 1.5 μm, and 1.0-3.0 μm, respectively. Cyclic voltammetries (CVs) in sulfuric acid demonstrated that attachment of SWNTs on 4-ATP/Pt is markedly stable, even after 30 potential cycles. CV in ruthenium hexamine was similar to bare Pt electrodes, suggesting that SWNTs assembly is similar to a closely packed microelectrode array.